A process for the synthesis of alkyl 3-amino-4-substituted benzoates has hitherto been investigated, in which alkyl esters derived from a 3-nitro-4-substituted benzoic acid undergo amination through reduction. However, when catalytic reduction is applied to a 3-nitro-4-halogenobenzoic acid, the active halogen atom adjacent to the nitro group of the acid is liable to be eliminated, which makes it difficult to produce the desired products in high yields. Although a conventional procedure of reduction in which iron powder is used ensures formation of the desired products from a 3-nitro-4-alkoxy-benzoic acid, the procedure requires complicated operations such as disposal of the iron powder. As a result, the esterification of a commercially readily available 3-amino-4-substituted benzoic acid by the Fischer method has been attempted. However, in the esterification, alkylation of the amino group also simultaneously takes place to give the desired products only in low yields.